JPS6017460B2 - Coating compositions containing esters of diglycidyl polyethers of saturated phenols - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel ester-containing coating compositions.

More particularly, the present invention relates to coating compositions containing esters of diglycidyl polyethers of saturated phenols. Recently, attention has been paid to the pollution effects and health effects associated with the use of organic solvents.

Many useful coating compositions contain significant amounts of organic solvents. Precautions when using the coating composition 2 These concerns were alleviated to some extent by the installation of a solvent recovery device. However, it would be even more desirable if coating compositions could be formulated that contain little or no organic solvents. Various attempts have been made to lower the organic solvent content in coating compositions.

A series of studies have focused on using water as the liquid medium instead of organic solvents. However, this method required changing the formulation of the resin and thus changing the performance obtained from the resin composition. Another line of work was directed toward formulating coating compositions with high solids content and therefore low organic solvent content. A problem with many of the high solids content coating compositions is that such compositions are usually very sticky and difficult to apply by conventional coating methods. It would be most preferred if a low organic solvent content coating composition could be formulated that also has a viscosity that provides a composition that can be applied in the prior art. If properly formulated into a coating composition, it can be easily applied;
Compounds have been found that produce coatings with desirable properties.

All percentages and ratios used herein are by weight unless otherwise specified.

The esters used in the coating compositions of the present invention are each epoxy of a diglycidyl polyether of phenol saturated with about 0.5 to about 1.5 equivalents of a saturated monocarboxylic acid and the aromatic nucleus of the phenol. It is a reaction product with a group.

The above esters are particularly useful when combined with a cross-linking agent selected from the group consisting of aminoplasts, isocyanates, blocked isocyanates, phenoplasts, and mixtures thereof to form coating compositions.

The coating composition has an organic solvent content of less than about 40 percent. Next, the ester of diglycidyl polyether of saturated phenol, its production method, and its use in coating compositions will be described.

The estels used in the coating compositions of the present invention have an idealized structural formula, where R has 1 to 4 carbon atoms and n is such that the average molecular weight of the jepoxide is from about 350 to about 3000. There are various numbers.

) is made from diglycidyl polyether of phenol.

These compounds are commercially available and can be made by reacting a suitable diphenol compound with epihalohydrin followed by hydrogenation of the aromatic nucleus.

Examples of diphenol compounds include bis(4-hydroxyphenyl)methane, i.e., bisphenol F; 1,1-
Bis(4-hydroxyphenyl)ethane; 2,2-bis(4-hydroxyphenyl)propane, or bisphenol A; and 1,1-bis(4-hydroxyphenyl)
It's butane. 2,2-bis(4-hydroxyphenyl)propane is preferred.

Suitable epihalohydrins include epichlorohydrin and ebipromhydrin. Catalysts suitable for use in the reaction of diphenolic compounds with epihalohydrin include tertiary amines such as triethylamine, tri-n-propylamine, penzyldimethylamine, N,N-dimethylaniline, and triethylamine, quaternary ammonium Hydrooxide, quaternary ammonium halide:
Alkali halides such as lithium chloride, potassium chloride and sodium chloride: and hydrazine with tertiary nitrogen atoms.

- As a general rule, the reaction between the diphenyl compound and epihalohydrin is carried out at elevated temperatures, e.g. from about 60 qC to about 200°C.
It happens. The hydrogen halide remover used is generally a strong alkali, such as anhydrous sodium hydroxide or concentrated sodium hydroxide solution. However, other alkaline reagents such as potassium hydroxide, barium hydroxide, sodium carbonate, or potassium carbonate can also be used to make diglycidyl compounds. The above reaction product was produced on August 15, 1967.
Hydrogenation is carried out by known methods such as those disclosed in US Pat. The above hydrogenated compound esters are made by reacting the hydrogenated compound with a carboxylic acid.

Such carboxylic acids are saturated monocarboxylic acids having 1 to 1 solid carbon atoms. Examples of such acids include acetic acid,
Includes propionic acid, butyric acid, caproic acid, myristic acid, valmitic acid, stearic acid, neododecanoic acid, dodecanoic acid, and belargonic acid. Hydrogenated carboxylic acids are also useful and can be used alone or in combination with any of the acids listed above. The hydroxyl group of the carboxylic acid further provides a site for curing with the cross-linking agent described below. Examples of carboxylic acids substituted with hydroxyl groups include 12-hydroxystearic acid,
Included are 2,2-dimethylolpropionic acid, 4-hydroxybutyric acid, 5-hydroxycaproic acid, glycolic acid, and lactic acid. Monocarboxylic acids having 4 to 1 carbon atoms are preferred.

Particularly preferred carboxylic acids are berargonic acid, neodecanoic acid, 12-hydroxystearic acid, and 2,2-dimethylic acid. propionic acid and mixtures thereof. The amount of monocarboxylic acid to react with the diglycidyl polyether of the hydrogenated phenol is from about 0.5 to about 1.5, based on the epoxy groups in the hydrogenated diglycidyl polyether phenol. The acid ranges from about 0.8 to about 1.2 equivalents.

The resulting reaction product has a hydroxyl group on the molecule for further reaction with the cross-linking agent described below. Ester formation occurs at temperatures of about 5°C to about 200°C with or without the use of solvents.

Any suitable catalyst such as a tertiary amine, quaternary ammonium hydroxide, quaternary ammonium halide or lithium carbonate can be used. The above esters have relatively low molecular weights and are substantially non-volatile when exposed to high temperatures.

The ester can also be diluted with a relatively small amount of organic solvent to reduce its viscosity. This property makes the ester particularly useful in coating compositions where only small amounts of organic solvents are available. Coating compositions can therefore be formulated from this ester and a suitable cross-binder with or without the use of small amounts of organic solvents. The resulting composition has a low viscosity and can be applied by conventional coating methods. Furthermore, the coatings obtained from this composition are durable, have a good appearance and a high degree of gloss. Coating Compositions The coating compositions of the present invention consist essentially of about 5 to 90 percent of the above esters, preferably about 10 to about 50 percent of the above esters, and about 5 to 80 percent, preferably about 20 to about 60 percent. of a suitable cross-linking agent.

Examples of crosslinking agents are aminoblasts, isocyanates, blocked isocyanates, phenoplasts and mixtures thereof. Preferred are aminoplasts and blocked isocyanates. The crosslinking agents mentioned above are discussed in more detail in the next section. Aminoplast resin is a substance containing formadehyde and amide/mono- or amide-groups,
For example, the main components are additive products with urea, ethylene diurea, ethylene urea, melamine, and benzoguanamine.

Condensation products resulting from the reaction of alcohol and formaldehyde with melamine, urea or penzoguanamine are preferred in the compositions of the invention. Useful alcohols used in making the etherification products are monohydric alcohols such as methanol, ethanol, propanol, butanol, benzyl alcohol and butoxetanol. Etherified melamine formaldehyde resins are preferred aminoplast resins. U.S. Patent No. 4,075,141, issued March 21, 1978, to Poer et al., describes useful aminoplast resins. Isocyanates useful as cross-linking agents include any of the many organic isocyanates available, such as p-phenylene diisocyanate, biphenyl isocyanate, toluene diisocyanate, 3,3'-dimethyl-4. 4'-bienylene diisocyanate, 1.4-tetramethylene diisocyanate, hexamethylene diisocyanate, 2,
2,4-trimethylhexane-1,6-diisocyanate, methylenepis(phenyl isocyanate), isophorodiisocyanate, 1,2,4-benzene triisocyanate, polymethylene polyphenyl isocyanate, bis(isocyanatecyclohexyl)methane and methylcyclohexyl Includes isocyanates and their derivatives.

Contains substantially no free isocyanate groups.

Blocked isocyanates, which are relatively inert at room temperature, are very useful crosslinking agents. Typical blocking agents are phenols, thiols, oximes, caprolactam and secondary aromatic amines. Many of these compounds are commercially available. ○． Day. Solomon
) written by Robert E. “The Chemistry of Organic Film-Forming Agents” published by Krieger Publishing Co., Ltd. (copyright 1977).
Nos. 216-21 of ilmFo err describe a number of blocked isocyanates that can be used in the coating compositions of the present invention. Phenoplast resins include condensation products of aldehydes and phenols.

Formaldehyde is the preferred aldehyde. Various phenols, such as phenol itself, cresol, p-phenylphenol, p-tert-butylphenol, P-
Tertiary amylphenol and cyclobentylphenol can be used. Particularly useful are the methylolphenol ethers described in US Pat. No. 2,597,33. The coating composition consists essentially of the ether and crosslinking agent described above.

Generally, however, the composition will include coating composition additives. Solvents such as water or organic solvents such as ketones, ethylene glycol monoalkyl ether acetates, esters and mono- and dialkyl ethers of propylene glycol, xylene, toluene and lower alcohols are used. However, it is preferred that the amount of organic solvent in the composition be less than about 40%, and more preferably less than about 30%, based on the composition. Other coating composition additives include pigments, fillers, antioxidants, flow control agents, surfactants, soot and reactive diluents. Preferred flow control agents are about 0.01 to about 40 microns, preferably about 0.0 microns.
These microgel particles are cross-polymerized microparticles having a particle size ranging from 1 to about 10 microns, most preferably from about 0.1 to about 5 microns.
2472:3iso0796:3966667:39924
86; 4025474; and 4147 Nezumi and British Patent No. 967051 are useful in the present invention. Particularly preferred are the dispersions described in US Pat. No. 4,147. These agents are included at levels ranging from about 0.1 to about 25% of the coating composition. Other curable resins can also be included in the composition. The coating composition is applied by any commonly used method including spraying, dipping and flow coating. This composition has been found to be particularly useful for coating metal substrates where solvent resistance, moisture resistance, and weather resistance are important, such as automotive parts. The following Reference Examples and Examples are intended to illustrate the above invention.

Reference Example 1 A 5-liter reaction flask was equipped with a heating means, a flywheel, and a nitrogen release odor.

Initially, a flask was charged with 172 grams of hydrogenated diglycidyl ether of 2,2-bis(4-hydroxyphenyl)propane (available as DRH-151.1 from Shell Chemical Company), 127 grams of neodecanoic acid, and A dimethyl-cocoamine linkage was added. The reaction mixture was heated to 12°C and exothermed to about 140°C. The mixture was kept at 140° C. for approximately 3 hours until an oxidation of less than 2 was obtained. The resulting mixture has a Gardner-Holdt viscosity of Z-6 to Z-7 and an acid value of 0.
It has a hydroxyl value of 148.9. Reference Example D A 3 liter reaction flask was lined as in Reference Example 1.

In this flask, jepoxyside of Reference Example 1 of 87 Crab,
112 base 12-hydroxystearic acid and acid dimethyl-cocoamine were added. The reaction mixture was heated to 115° C. and an exotherm of 12 mm was generated while maintaining a nitrogen atmosphere.

The reaction mixture was stirred at 140° C. until an acidity lower than 2.
It was kept for about 8 hours.

The above reaction mixture has a Gardner-Holdt viscosity x, oxidation 1.
It has a 9K acid value of 197.7.

Reference example m In a 3-liter reaction flask set up as in Reference example 1,
1167g of Jepoxide used in Reference Example 1, 95
Females received neodecanoic acid, 8 cycles of dimethylolpropionic acid, and fins received dimethyl-coco-amine.

The reaction mixture was heated to 115 qo with an exotherm of about 12 qo. The mixture is kept at this temperature for about 4 hours until an acid number below 1 is obtained. The resulting reaction mixture has a Gardner-Holdt viscosity Z, an acid number of 0.7 and a hydroxyl number of 178.3.

EXAMPLE 1 A coating composition is formulated as follows/G-CENT Ester of Reference Example D 14.3 Methylolated Melamine Formaldehyde Condensate '1'
22.8 Microgel dispersion [21
12.9 Pigment paste [31
5.9 Acrylic resin ■
19.1 Diisopro/gunolamine p
-Toluenesulfonic acid hydrochloride 0.4 diisopropanolamine phosphate phenyl salt
0.2-substituted penzotriazole [51
1.1 Butylacetate
233'11 The methylolated melamine-formaldehyde condensate was manufactured by American Cyanamid Company (A
mehcan C〆namid CO. ) to
Cymel 303 is an aminoplast resin commercially available as Cymel 303.

[21 Microgel dispersion is disclosed in U.S. Patent No. 4147688
Example 0' of No. 1 corresponds to the dispersion described here.

'3' Pigment paste is 183% aluminum paste; Pigment grinding resin 13.6% consisting of 10% hydroxyethyl acrylate, 4% methacrylic acid, 20% styrene, 15% butyl acrylate and 51% isobutyl methacrylate: 25.8 % ethylene glycol monoethyl ether acetate; 1.5% butanol; 0.4%
Isopropanol; and 20.2% toluene: and 20
．． Contains 2% high flash naphtha. '41 Same resin as pigment paste resin.

[5' Ciba-WigyCor
p. It is commercially available as Tinuvin 328 from ). The above composition has a viscosity of 22 seconds as measured in a #4 Ford Cup at 24q.

This composition is easily applied to metal panels with a spray device.

After being applied to the coated panel for 30 minutes at 120 pm, it has an acceptable appearance and is sag resistant, solvent resistant, acid resistant and water immersion resistant compared to enamels used on the market. Superior. Example 0 The following composition was blended.

/ Gucent Reference Example 1 Estel 17.9 Aminoplast Resin [1' 17.9 Pigment Paste [2' 33.1 Acrylic Resin Leg 10.12,
2-dimethyl-3-hydroxypropyl-2,2-dimethyl-3'-hydroxypropionate'4}
9.0 Microgel dispersion {31 8.0 Penzotriazole 1.3 Diisopropanolamine p-toluenesulfonate
1.1 diisopropanolamine phenyl phosphate 0.4 eta/l
0,4 methyl amyl ketone 0.8 {11 Monsanto Co. (Moman CO.) mustard dimene (Re
Melamine resin commercially available as simene) 755.

[2' Pigment paste is 67% titanium dioxide: 10% hydroxyethyl acrylate, 25% methacrylic acid (contains 25% methacrylic acid reacted with hydroxyethyl thylenimine) 30% styrene, 20% 2-ethylhexyl Acrylate, milled resin 1 made from 19.5% butyl methacrylate and 18% methyl methacrylate
2%: and 21% solvent.

'3' Used in Example 1.

'41 Union Carbide
deCorp. ) to ester diol (EsterD
iol) 204.

The above composition has a viscosity of 29 sand in a #4 food cup.

This composition was applied as a spray and tested as in Example 1 to provide a durable coating on metal panels.

Claims (1)

[Claims] 1 (a) Reaction of each epoxy group in diglycidyl polyether of phenol in which the aromatic ring of phenol is saturated with about 0.5 to about 1.5 equivalents of saturated monocarboxylic acid. consisting more essentially of about 5 to about 90% of the product; and (b) about 5 to about 80% of a cross-linking agent selected from the group consisting of aminoplasts, isocyanates, blocked isocyanates, phenoplasts, and mixtures thereof. Coating composition. 2. The composition of claim 1, wherein the composition contains less than about 40% organic solvent. 3 Diglycidyl polyether of phenol is bis(
4-hydroxyphenyl)methane, 1,1-bis(4-
selected from the group consisting of hydrogenated diglycidyl polyethers of hydroxyphenyl)ethane, 2,2-bis(hydroxyphenyl)propane and 2,2-bis(4-hydroxyphenyl)butane and mixtures thereof. A composition according to claim 1. 4 Diglycidyl polyether of phenol is 2,2-
Claim 3 is a hydrogenated diglycidyl polyether of bis(4-hydroxyphenyl)propane.
The composition described in Section. 5. A composition according to claim 1, 3 or 4, wherein the monocarboxylic acid has 1 to 18 carbon atoms. 6 About 0.8 to about 1.2 equivalents of 4 to 18 carbon atoms
6. The composition of claim 5, wherein a monocarboxylic acid having a phenolic acid is reacted with each epoxy group in the diglycidyl ether of phenol. 7. The composition according to claim 1, wherein the cross-linking agent is an aminoplast. 8. The composition according to claim 1, wherein the crosslinking agent is a blocked isocyanate. 9. The composition of claim 1, wherein the ester represents from about 10 to 50 percent of the composition and the crosslinker represents from about 20 to about 60 percent of the composition. 10. The composition of claim 9 further consisting of about 0.1 to about 2.5% microgel dispersion flow control agent.